Asphaltene hydroconversion process

ABSTRACT

AN ASPHALTENE HYDROCONVERSION PROCESS FOR THE CONVERSION OF ASPHALTENES TO LOWER BOILING HYDROCARBONS BY CONTACTING SAID ASPHALTENES WITH HYDROGEN IN THE PRESENCE OF A SOLID POLYMER PREPARED BY INTERACTING AN AROMATIC POLYCARBOXYLIC ACID ANHYDRIDE OR HALIDE PRODUCING COMPOUND WITH A POLYNUCLEAR AROMATIC COMPOUND.

United States Patent 3,592,761 ASPHALTENE HYDROCONVERSION PROCESS EdwardL. Cole, Fishkill, and Edwin C. Knowles, Poughkeepsie, N.Y., assignorsto Texaco Inc., New York,

No Drawing. Filed Apr. 14, 1969, Ser. No. 816,105 Int. Cl. (310g 13/02US. Cl. 208108 11 Claims ABSTRACT OF THE DISCLOSURE An asphaltenehydroconversion process for the conversion of asphaltenes to lowerboiling hydrocarbons by contacting said asphaltenes with hydrogen in thepresence of a solid polymer prepared by interacting an aromaticpolycarboxylic acid anhydride or halide producing compound with apolynuclear aromatic compound.

This invention relates to a hydroconversion process for increasing theyield of lower boiling hydrocarbons and more particularly tohydrocracking process wherein an asphaltene containing heavy hydrocarboncharge stock is contacted with hydrogen in the presence of a solidpolymer prepared by the interaction of an aromatic polycarboxylic acid,anhydride or halide producing compound with a polynuclear aromaticcompound.

Generally, hydrocracking finds its highest degree of utility in thecracking of hydrocarbons boiling in the heavy naphtha and light gas oilrange. It has however met with only limited acceptance in the upgradingof heavy hydrocarbon oils, particularly those containing high boilingasphaltenes and substantial sulfur and nitrogen contents such as totalcrude oil, topped crudes and residua, shale oil, coal tars, etc. Thevarious sulfur and nitrogen compounds present in such oils tend topoison the hydrocracking catalyst and to deposit coke during catalytichydrocracking operation, whereas the conversion of asphaltenes isaccompanied by the deposition of coke and metals. It has beenparticularly found that the higher boiling petroleum fractions of suchoils, i.e. those fractions boiling above about 750 F., and particularlyabove about 850 F., at atmospheric pressure contain relatively highproportions of the above-mentioned asphaltenes and objectionablecontaminating materials. Accordingly, conventional hydrocracking of suchfractions, or of oil feeds containing such fractions, has proved to beof very limited effectiveness.

It will be appreciated, therefore, that there is presently a highincentive for discovering a successful means for hydrocracking heavyhydrocarbon stocks containing asphaltenes to valuable lower boilingproducts.

It is therefore an object of this invention to provide an improvedprocess for hydrocracking such feeds whereby higher yields of lowerboiling hydrocarbons are obtained without substantial deposition ofcoke.

It has now been found that lower boiling hydrocarbons can be obtainedfrom an asphaltene containing heavy hydrocarbon charge stock by the useof a process which comprises contacting said heavy hydrocarbon chargestock with hydrogen in the presence of a promoting amount of a solidpolymer for a time sufiicient under hydrogen contact conditions ofpressure and temperature to convert at least a portion of theasphaltenes to lower boiling hydrocarbons and recovering lower boilinghydrocarbons wherein said solid polymer is prepared by the process whichcomprises interacting an aromatic polycarboxylic compound with apolynuclear aromatic compound. Thus it has been discovered that thehydrogen contact step in the presence of a solid polymer prepared byinteracting an 'ice ess, and regenerated for further continued use.

In general the process of this incention is carried out by contactingthe asphaltene containing heavy hydrocarbon charge stock with hydrogenin the presence of a promoting amount of solid polymer prepared byinteracting an aromatic polycarboxylic compound with a polynucleararomatic compound, hereinafter referred to as solid polymer. The termpromoting amount is used herein to be that concentration by weight ofpromoter which during the hydrogen contact step produces a yield oflower boiling hydrocarbons from asphaltenes greater than the yield oflower boiling hydrocarbons from asphaltenes obtained in the absence ofthe solid polymer. In general a concentration of solid polymer of fromabout 0.5% to about 20%, more preferably from about 2.0% to about 15%based upon the weight of the heavy hydrocarbon charge stock is utilizedduring the hydrogen contact step. The lower boiling hydrocarbonfractions are then recovered from the charge stock by conventionalmeans, such as by distillation or vacuum stripping optionally using aninert stripping gas.

The conditions for hydrogen contact can be varied over a wide range asto liquid hourly space velocity (LHSV, volume of feed to volume ofcontactor per hour), hydrogen gas rate (volume of hydrogen to volume ofheavy hydrocorbon charge stock, s.c.f./bbl.), temperature, pressure andthe concentration of solid polymer. These conditions are adjusted inorder to produce a hydrogen conaromatic polycarboxylic compound with apolynuclear tact step wherein the hydrogen and solid polymer promoterare present in a concentration sufiicient to elfect production of lowerboiling hydrocarbons and are adjusted in order to maximize the yield oflower boiling hydrocarbons from the heavy hydrocarbon fraction whileminimizing any carbon or coke formation.

It is contemplated within the scope of this invention that the processwhen practiced on a continuous basis can provide for recycle ofnon-converted asphaltenes to the charge stock for reprocessing. By theuse of the term without substantial formation of coke is meant that theprocess of this invention provides for less than 0.35% by weight cokeformation as a function of the total weight of asphaltenes present inthe charge stock still more preferably less than 0.06 wt. percent cokeformation.

The heavy hydrocarbon charge stock is contacted with hydrogen in thepresence of the solid polymer in general at a temperature of from about550 F. to about 900 F. preferably from about 725 F. to about 850 F.;pressures of from about 1000 to about 6000 psig preferably from about2000 to about 5000 p.s.i.g.: liquid hourly space velocities of fromabout 0.1 to about 10 preferably from about 0.5 to about 2.5 volumes offeed per volume of contactor void space per hour; and hydrogen rates offrom about 500 to about 20,000 preferably from about 2500 to about10,000 standard cubic feet (s.c.f.) per barrel of feed.

In general the solid polymers which are utilized for the conversion ofasphaltenes are prepared by the interaction of an aromaticpolycarboxylic compound preferably an aromatic polycarboxylic acid,anhydride and/ or halide producing compound with a polynuclear aromaticcompound preferably in the presence of a Friedel-Crafts catalyst.Generally, molar ratios of the polynuclear aromatic compound (forcompounds having a molecular weight less than about 1000) to thearomatic carboxylic acid, anhydride or halide compound is from about 0.5to 1 to about 4 to 1 more preferably from about 1 to 1 to about 3 to 1.For polynuclear aromatic compounds having molecular weights of about1000 or greater such as petroleum cokes and asphaltenes it is preferredto use weight ratios of polynuclear aromatic compounds to the aromaticcarboxylic acid anhydride or hydride compound of about 0.1 to 1 to about3 to 1, more preferably from about 0.5 to 1 to about 2 to 1. Inpreparing the solid polymers it is preferred to use a Friedel-Craftscatalysts such as zinc chloride, aluminum chloride, aluminum bromide andferric chloride. In general the catalyst is used at a concentration offrom about 0.5 to 4.0 moles of catalyst per mole of aromaticpolycarboxylic compound, more preferably from about 0.75 to 2.5 moles ofcatalyst per mole of aromatic polycarboxylic compound. The reactionconditions as to temperature and time can be varied over a wide range,those conditions being utilized which produce the solid polymer. Ingeneral, temperatures of from about 350 F. to about 700 F. morepreferably from about 450 F. to about 625 F., for from about 0.5 hoursto about 24 hours more preferably from about 1 hour to about 12 hoursare utilized. The solid polymers can be recovered from the reactionmixture by conventional means and in addition can be washed with diluteaqueous acid solutions. Typical procedures for preparing the solidpolymers are set forth in the articles Pohl, H. A. and E. H. Enhelhardt,J. Physical Chemistry 66, 2095 (1962), and Pohl, H. A. and D. A. Opp, J.Physical Chemistry 66, 2121 (1962), which articles are therebyincorporated by reference. It is preferred that the solid polymer whenutilized in the process of this invention have a particle size fromabout 20 microns to about 500 microns more preferably from about 100microns to about 250 microns, although particle sizes above and belowthough set forth above can be utilized in the process of this invention.

Typical examples of aromatic polycarboxylic compounds are represented bythe structural formula:

wherein Ar is an aromatic nucleus, each R is independently selected fromthe group consisting of OH, halide, a lower hydrocarbonoxy radicalhaving from about 1 to about 12 carbon atoms and any two groupsrepresented by which are attached to adjacent carbon atoms on Ar cantogether form together form (l H o In a still more preferred embodimentof this invention, I; is from zero to two, more preferably b is zero andR is selected from OH, chloride and when two groups represented bytogether form When 12 is greater than zero it is preferred that R havefrom 1 to about 16 carbon atoms more preferably from 1 to about 8 carbonatoms and still more preferably from 1 to about 3 carbon atoms. Typicalexamples of aromatic nucleus are benzene, naphthalene, anthracene,biphenyl and terphenyl. It is preferred that the aromatic nucleus isselected from benzene, naphthalene and biphenyl, more preferably thatthe aromatic nucleus is benzene.

Typical examples of hydrocarbon radicals which are attached to the oxyradical to form hydrocarbonoxy radicals representing R and hydrocarbonradicals representing R are alkyl such as methyl, ethyl, butyl, t-butyl,3-methyll-pentyl, n-octyl and those aliphatic radicals which representthe hydrocarbon portion of a middle distillate or kerosine, cycloalkylradicals such as cyclopentyl, alkylated cycloalkyl radicals such as monoand polymethylcyclopentyl radicals, aryl and cycloalkyl substitutedalkyl radicals such as phenylethyl and cyclohexylpropyl, alkylphenylsubstituted alkyl radicals examples of which are benzyl, methylbenzyl,caprylbenzyl, phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl,aryl radicals such as phenyl, and naphthyl, alkaryl radicals such asxylyl, alkylphenyl, and ethylphenyl. In addition, any groups representedby R that remain in the solid polymers and R are defined as hydrocarbonradicals which are noninterfering with respect to the promoting activityof the solid polymer promoter. By non-interfering is meant that thesubstituents representing R and R' do not completely nullify theactivity of the solid polymer promoter during the hydrogen process step.

Typical examples of aromatic polycarboxylic acid and anhydride producingcompounds are phthalic anhydride, m-phthalic acid, terephthalic acid,pyromellitic anhydride, trimellitic anhydride, pyromellitic acid,trimellitic acid, dimethyl terephthalate, diisopropyl terephthalate,dibenzyl terephthalate and dimethylophthalate.

In general the polynuclear aromatic compounds contain a plurality ofaromatic rings. A particularly preferred class of polynuclear aromaticcompounds are those having a molecular weight below 1000 and in additionpolynuclear aromatic compound which contain from 2 to about 9 aromaticrings, preferably fused aromatic rings.

Typical examples of polynuclear aromatic compounds are trans-stilbene,fiuoroene, 1,2-benzfluorene, 1,2,3,4 peridinaphthalene fluorene, 9,9bifluorenyl, 9,9 bifluorylidene, acenaphthene, acenaphthylene,anthracene, 9,10 dihydroanthracene, 9,10 dimethylanthracene, 2-methylphenanthrene, naphthacene, 5,12 dihydronaphthacene,1,2-benzanthracene, 7,12 dimethyl 1,2 benzanthracene,1,2,5,6-dibenzanthracene, chrysene, pyrene, 1,2,6,7 tetrahydropyrene, 4methylpyrene, 3,4 benzpyrene, 1,2,4,5,8,9 tribenzpyrene, perylene,1,12-benzperylene, pentacene, 1,2,8,9 dibenzpentacene coronene,acridine, 1,5 dihydroxyanthraquinone, 1,8 dihydroxyanthraquinone, 1,4dihydroxyanthraquinone, 1,2 dihydroxyanthraquinone, 1hydroxyanthraquinone, 1,4,9,10- tetrahydroxyanthracene, 1,4dihydroxynaphthalene, 2,7- dihydroxynaphthalene, 2,3dihydroxynaphthalene, 6- bromo 2 naphthol, 1 bromo 2 naphthol,7-acenaphthol, 9 bromophenanthrene, carbazole, phenolphthalein, pniaphtlholbenzine, 2 lbromo e phenylphenol, dibenzanthrone(violanthrone), p,p' diphenol, 1,4 diphenylpiperazine, 1,8dihydroxyanthraquinone, 1,5 dihy-droxyanthraquinone, 1,8dihydroxyanthraquinone, 1,4 dihydroxyanthraquinone, 1,2dihydroxyanthraquinone, 1 hydroxyanthraquinone,1,4,9,10-tetrahydroxyanthracene, 1,4 dianthraquinonylaminoanthraquinone,1,4-dihydroxynaphthalene, l-bromo-Z-naphthol.

In addition it is contemplated within the scope of this invention toutilize coke as an aromatic compound, such as asphaltic coke and carboidcoke. Thus the coke can be produced by conventional coking means such asby delayed coking processes or fluid coking processes which processesare well known in the art. Various types of cokes which are contemplatedwithin the scope of this invention are described in Carbon and GraphiteHandbook by C. L. Mantell, Interscience 1968 which article isincorporated by reference. In addition it is contemplated within thescope of this invention that asphaltenes can be used as the aromaticcompound for the preparation of the solid polymer. Such asphaltenes arein general prepared by the extraction of asphalts utilizing aromaticsolvents. Asphaltenes are generally classified as those materials whichare soluble in aromatic solvents and insoluable in n-paraflins.

A wide variety of asphaltene containing heavy hydrocarbon fractions maybe treated, or made suitable for further processing, through theutilization of the method encompassed by the present invention. Suchheavy hydrocarbon fractions usually contain from about 0.5 to about 10.0Wt. percent asphaltenes and include full boiling range crude oils,topped or crude oils, vacuum tower bottoms, and visbreaker bottomsproduct. The present method is particularly well adaptable to thetreating of crude oils and topped or reduced crude oils containing largequantities of asphaltenic material, and is especially advantageous whenapplied to the treating of atmospheric or vacuum towers bottoms e.g.especially 550 F. or higher atmospheric reduced crude oils.

The present invention can be carried out in batch, continuous orsemi-continuous operating cycles, and in one or more actual ortheoretical stages, employing contacting and separation equipment suchas has heretofore been employed in hydrocracking of petroleum stocks. Inaddition a multi-stage mode of operation that is a repeating of theprocess several times can be utilized in carrying out the process ofthis invention.

The process of this invention can be better appreciated by the followingnon-limiting examples.

EXAMPLE 1 To a glass liner reactor is added 100 grams of pyrene and 108grams of pyromellitic dianhydride. To this mixture is added withagitation 136 grams of zinc chloride. The reactor is flushed withnitrogen and heated to 500 F. under atmospheric pressure. A temperatureof 495 F. is then maintained for a period of 24 hours. The temperatureis reduced to ambient temperature and 258.5 grams of a shiny blackbrittle solid polymer is obtained. The polymer is powdered and extractedthree times with 1000 milliliter portions each of a 4 wt. percenthydrochloric acid solution allowing about 24 hours extraction time foreach extraction. The product is then filtered and extracted with waterfor 25 hours, followed by extraction with ethanol for 40 hours andbenzene for 24 hours. A solid polymer is then recovered Which weighs 165grams.

6 EXAMPLE 2 To a glass lined reactor is added 53.5 grams of anthraceneand 40.2 grams of phthalic anhydride. To this mixture is added withagitation 81.8 grams of zinc chloride. The reactor is flushed withnitrogen and heated to 500 F. under atmospheric pressure. A temperatureof 495 F. is then maintained for a period of 24 hours. The temperatureis reduced to ambient temperature and 135.7 grams of a shiny, black,brittle solid polymer is obtained. The polymer is powdered and extractedthree times with 500 milliliter portions each of a 4 wt. percenthydrochloric acid solution allowing about 24 hours extraction time foreach extraction. The product is then filtered and extracted with waterfor 25 hours, followed by extraction with ethanol for 40 hours andbenzene for 24 hours. A solid polymer is then recovered which weighs57.2 grams.

EXAMPLE 3 To a glass lined reactor is added 62.5 grams of anthraquinoneand 44.4 grams of phthalic anhydride. To this mixture is added withagitation 81.8 grams of zinc chloride. The reactor is flushed withnitrogen and heated to 500 F. under atmospheric pressure. A temperatureof 500 F. is then maintained for a period of 24 hours. The temperatureis reduced to ambient temperature and a shiny black brittle solidpolymer is obtained. The polymer is powdered and extracted with 19-2000milliliter portions each of a 4 wt. percent hydrochloric acid solutionallowing about 24 hours extracting time for each extraction. The productis then filtered and extracted with water until free of chloride ion,followed by extraction with ethanol for 12 hours and benzene for 18hours. A solid polymer is then recovered which weighs 39.8 grams.

EXAMPLE 4 To a glass lined reactor is added 107 grams of anthracene and80.4 grams of phthalic anhydride. To this mixture i added with agitation195 grams of ferric chloride. The reactor is flushed with nitrogen andheated to 500 F. under atmospheric pressure. A temperature of 495 F. isthen maintained for a period of 24 hours. The temperature is reduced toambient temperature and a shiny black brittle solid polymer is obtained.The polymer is powdered and extracted seven times with 2000 milliliterportions each of a 4 wt. percent hydrochloric acid solution allowingabout 24 hours extraction time for each ex traction. The product is thenfiltered and extracted with water until free of chloride ion, followedby extraction with ethanol for 12 hours and benzene for 50 hours. Asolid polymer is then recovered which weights 70 grams.

EXAMPLE 5 To a glass lined reactor is added grams of a coke from delayedcoking mid continent stocks (less than 100 mesh) having the followingproperties:

Sulfur, wt. percent 1.29 Ash, wt. percent 1.27 Hydrogen, wt. percent 3.9Nitrogen, wt. percent 1.2 Surface area, mfl/gram 5.0

and 108 grams of pyromellitic dianhydride. To this mixture is added withagitation 136 grams of zinc chloride. The reactor is flushed withnitrogen and heated to 500 -F. under atmospheric pressure. A temperatureof 500 F. is then maintained for a period of 24 hours. The temperatureis reduced to ambient temperature and 248 grams of a shiny black brittlesolid polymer is obtained. The polymer is powdered and extracted 10times with 2000 milliliter portions each of a 10 wt. percenthydrochloric acid solution allowing about 24 hours extraction time foreach extraction. The product is then filtered and extracted w th waterfor 24 hours, followed by extraction with ethanol for 24 hours, benzenefor 24 hours. A solid polymer is then recovered which was re-extractedwith 30,000 ml. of wt. hydrochloric acid solution, extracted with wateruntil free of chloride ion followed by extraction with ethanol. Thepolymer was dried and 68 grams were recovered.

EXAMPLE 6 960 grams of a mid-continent asphalt (penetration 56 at 77 F.)is put into solution with 920 grams of benzene. The solutioin is mixedwith 10,500 ml. of n-pentane and allowed to settle overnight. Thepentane layer is decanted from a particulate layer of asphaltenes. Thislayer is filtered, washed with n-pentane and dried. A product, 171 gramsof coffee-brown material that had the following analysis is recovered.

Hydrogen, wt. percent 7.6 Nitrogen, wt. percent 1.0 Sulfur, wt. percent6.2 Ash, wt. percent 1.1

100 grams of the above material is powdered and mixed with 108 grampyromellitic dianhydride. To this mixture is added with agitation 136grams of zinc chloride. The reactor is flushed with nitrogen and heatedto 500 F. under atmospheric pressure, a temperature of 500 F. is thenmaintained for a period of 24 hours. The temperature is reduced toambient temperature and 298 grams of a solid polymer is obtained. Thepolymer is powdered and extracted 12 times with 2700 milliliter portionseach of a 4 wt. percent hydrochloric acid solution allowing about 24hours extraction time for each extraction. The product is then filteredand extracted with water for hours, followed by extraction with ethanolfor hours, and benzene for 24 hours. A solid polymer is then recovered.

EXAMPLE 7 To a 1290 milliliter pressure rocking reactor equipped withgas addition means is added 502 grams of a California atmosphericreduced crude oil having the following properties:

Gravity API 15.2 Carbon Residue, wt. percent 8.54 Sulfur, wt. percent1.58 Total Nitrogen, wt. percent 0.74 DPI flask dist., wt. percent:

IB B -850 F. 38.1 Residue 850 F.+ 61.9

Wt. percent asphaltenes (in 850 F.+) material 9.54

together with grams of the solid polymer (50-150 microns) fromExample 1. The reactor is flushed with hydrogen and the temperature isincreased to 750 F. under a hydrogen atmosphere. A total pressure of4,000 p.s.i.g. is maintained at 750 F. for a period of 42 hours. Afterthis time the temperature is reduced to ambient temperature. It isdetermined that the hydrogen consumption based on the pressure drop is775 standard cubic foot per barrel of charge. The oil is recovered fromthe pressure reactor and filtered to recover the solid polymer catalyst.It is determined that there is no coke deposit formation.

EXAMPLE 8 To a 1290 milliliter pressure rocking reactor equipped withgas addition means is added 502 grams of a California atmosphericreduced crude oil the properties of which are set forth in Example 7together with 50 grams of the solid polymer (50 to microns) from Example2. The reactor is flushed with hydrogen and the temperature is increasedto 750 F. under a hydrogen atmosphere. A total pressure of 4,000p.s.i.g. is maintained at 750 F. for a period of 42 hours. After thistime the temperature is reduced to ambient temperature. It is determinedthat the hydrogen consumption based on the pressure drop in 1070standard cubic foot per barrel of charge. The oil is recovered from thepressure reactor and filtered to recover the solid polymer catalyst. Itis determined that there is no coke deposit formation.

EXAMPLE 9 To a 1290 milliliter pressure rocking reactor equipped withgas addition means is added 502 grams of a California atmosphericreduced crude oil the properties of which are set forth in Example 7together with 50 grams of the solid polymer (50 to 150 microns) fromExample 3. The reactor is flushed with hydrogen and the temperature isincreased to 750 F. under a hydrogen atmosphere. A total pressure of4,000 p.s.i.g. is maintained at 750 F. for a period of 29 hours. Afterthis time the temperature is reduced to ambient temperature. It isdetermined that the hydrogen consumption based on the pressure drop is720 standard cubic foot per barrel of charge. The oil is removed fromthe pressure reactor and filtered to recover the solid polymer catalyst.It is determined that there is no coke deposit formation.

EXAMPLE 10 To a 1290 milliliter pressure rocking reactor equipped withgas addition means is added 501 grams of a California atmosphericreduced crude oil the properties of which are set forth in Example 7together with 50 grams of the solid polymer (50-150 microns) fromExample 4. The reactor is flushed with hydrogen and the temperature isincreased to 750 F. under a hydrogen atmosphere. A total pressure of4,000 p.s.i.g. is maintained at 750 F. for a period of 42.5 hours. Afterthis time the temperature is reduced to ambient temperature. It isdetermined that the hydrogen consumption based on the pressure drop is930 standard cubic foot per barrel of charge. The oil is removed fromthe pressure reactor and filtered to recover the solid polymer catalyst.It is determined that there is no coke deposit formation.

EXAMPLE 11 To a 1290 milliliter pressure rocking reactor equipped withgas addition means is added 500 grams of a California atmosphericreduced crude oil the properties of which are set in Example 7 togetherwith 50 grams of the solid polymer (50-150 microns) from Example 5.

i The reactor is flushed with hydrogen and the temperature is increasedto 750 F. under a hydrogen atmosphere. A total pressure of 4,000p.s.i.g. is maintained between 750 to 765 F. for a period of 30 hours.After this time the temperature is reduced to ambient temperature. It isdetermined that the hydrogen consumption based on the pressure drop is760 standard cubic foot per barrel of charge. The oil is removed fromthe pressure reactor and filtered to recover the solid polymer catalyst.It is determined that there is no coke deposit formation.

EXAMPLE 12 To a 1290 milliliter pressure rocking reactor equipped withgas addition means is added 500 grams of a California atmosphericreduced crude oil the properties of which are set forth in Example 7together with 50 grams of the solid polymer (50-150 microns) fromExample 6. The reactor is flushed with hydrogen and the temperature isincreased to 750 F. under a hydrogen atmosphere. A total pressure of4,000 p.s.i.g. is maintained at 750 F. for a period of 42 hours. Afterthis time the temperature is reduced to ambient temperature. It isdetermined that the hydrogen consumption based on the pressure drop is680 standard cubic foot per barrel of charge. The oil is removed fromthe pressure reactor and filtered to recover the solid polymer catalyst.It is determined that there is no coke deposit formation.

EXAMPLE 13 Example 11 is repeated using the same amount of Californiaatmospheric reduced crude and 50 grams of (50-150 micron) coke fromdelayed coking Mid-continent stocks, the properties of which are setforth in Example 5. After a period of 46 hours at a temperature of 750F. and a hydrogen'pressure of 4,000 p.s.i.g. It is determined that aheavy carbon deposit is formed.

EXAMPLE 14 Example 7 is repeated except that the solid polymer isomitted from the process. After a period of 44 hours and a temperatureof 750 F. and a hydrogen pressure of 4,000 p.s.i.g. it is determinedthat a heavy carbon deposit is formed.

The test results on the oil product obtained from Examples 7 through 14are set forth below in Table I.

The autoclave appearance at the end of the run was obtained throughvisual inspection. The percent disappearance of asphaltenes wasdetermined by a modified procedure for deasphalting and deresinizing acrude oil described in Analytical Edition, Industrial and EngineeringChemistry, vol. 13, 1941, page 314. This procedure for determiningasphaltene concentration comprises heating a sample grams) together with100 milliliters of mixed hexanes. The liquid is filtered into a Gouchcrucible (asbestos lined) leaving behind that material which settledfrom the mixed hexanes. The settled material is copiously treated withwarm mixed hex-anes until a substantially water white filtrate isobtained. The solids which remain are then filtered into the Gouchcrucible which is rewashed until the color is water white. The Gouchcrucible containing asphaltenes is then air dried in an oven at 210 F.The difference in weight between the Gouch crucible before and after thehexane extraction is determined as the weight of asphaltenes from whichthe percent of asphaltenes is calculated.

The weight percent disappearance of asphaltenes is obtained by dividingthe difference between the weight percent asphaltenes in the charge andthe weight percent asphaltenes present after the process by the weightpercent asphaltenes present in the charge times 100.

A 108 wt. percent gain in calculated asphaltenes.

Clean.

3 Heavy carbon.

The results in Table I demonstrate the outstanding effectiveness of theprocess of this invention for converting asphaltenes which are presentin a hydrocarbon charge stock. More particularly, the process of thisinvention provides for the conversion of asphaltenes without theformation to any substantial degree of carbon or coke deposits. Thus theresults obtained in Examples 7 through 12 demonstrate that the solidpolymer produces asphaltene conversion while eliminating carbondeposits. These re sults are in sharp contrast to the low conversion andheavy carbon deposits utilizing a coke from delayed coking mid-continentstocks (Example 13) or Example 14 wherein a 108 weight percent increasein asphaltenes occurred together with carbon deposits when the polymerwas omitted.

While this invention has been described with respect to various specificexamples and embodiments it is to be understood that the invention isnot limited thereto and that it can be variously practiced within thescope of the following claims.

We claim:

1. A process for the conversion of an asphaltene containing heavyhydrocarbon charge stock which comprises contacting said heavyhydrocarbon charge stock with hydrogen in the presence of about 0.5% toabout 20% by weight based on the hydrocarbon charge stock of a solidpolymer for a time suflicient under hydrogen contact conditions of about1000-6000 p.s.i.g. pressure and 550-900 F. temperature to convert atleast a portion of the asphaltenes to lower boiling hydrocarbons andrecovering lower boiling hydrocarbons wherein said solid polymer isprepared by the process which comprises interacting an aromaticpolycarboxylic compound with a polynuclear aromatic compound.

2. A process of claim 1 wherein the polycarboxylic I compound isrepresented by the structural formula all.)

wherein Ar is an aromatic nucleus, each R is independently selected fromthe group consisting of -OH, halide, a lower hydrocarbonoxy radicalhaving from about 1 to about 12 carbon atoms and any two groupsrepresented y which are attached to adjacent carbon atoms on Ar cantogether form each R is a hydrocarbon radical, a is an integer having avalue of from 2 to 4 and b is an integer having a value of from 0 to 4provided that the sum of a+b is not greater than 6.

3. A process of claim 2 wherein b has a value of zero, R is selectedfrom the group consisting of alkoxy having from 1 to about 6 carbonatoms, OH, chloride and when two groups representing together form II o4. A process of claim 3 wherein R is selected from the group consistingof hydroxyl, chloride and any two groups representing matic compoundcontains from 2 to about 9 fused aromatic rings.

7. A process of claim 2 wherein the polynuclear aromatic compound isselected from the group consisting of coke, asphaltenes, and mixturesthereof.

8. The process of claim 1 wherein the solid polymer is prepared in thepresence of a Friedel-Crafts catalyst.

9. The process of claim 8 wherein the Friedel-Crafts catalyst isselected from the group consisting of zinc chloride, ferric chloride,aluminum chloride and mixtures thereof.

10. The process of claim 2 wherein the solid polymer is prepared in thepresence of a Friedel-Crafts catalyst.

11. The process of claim 10 wherein the Friedel-Crafts catalyst isselected form the group consisting of zinc chlo- UNITED STATES PATENTS3,338,854 8/1967 Hedge et al 26028 DELBERT E. GANTZ, Primary Examiner R.M. BRUSKIN, Assistant Examiner U.S. CL. X.R. 20s 44

